JPS5940138B2 - Olefin manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing olefins, and more particularly to a process for the catalytic conversion of lower alcohols and/or ethers.

ZS lower alcohol or ether or both
The use of the unique catalytic properties of a particular type of zeolite, classified as M-5, to convert it into aromatic-rich gasoline boiling range products has been published in the German Opening of Publication (DTOS).
It is known from No. 2438252.

By appropriately selecting the conditions for contacting the raw materials with the catalyst, the present inventors have made the reaction suitable for the production of olefins of 2 to 4 carbon atoms, which are of particular industrial interest. discovered that it could be modified to make it suitable for manufacturing. Alcohols and/or ethers having 4 or less carbon atoms per alkyl group according to the invention have a CONSTRAINTINDEX of 1.
,0 to 12.0, and the silica/alumina ratio is 12 to 300.
0, the crystal density in the dry hydrogen form is substantially no.
．． 67/CC or higher, wherein the partial pressure of the alcohol or the ether or both is reduced to atmospheric pressure during said contact. or (b) use as a catalyst a zeolite mixed with an inert solid diluent of at least an equal weight to the zeolite: a severity sufficiently low to thereby reduce the aromatization activity of the catalyst ( The contacting is performed at the following times.

``Severity'' refers to the degree of severity of a product by appropriately adjusting known factors that determine the rate and rate of reaction in chemical processes, such as temperature, pressure, concentration of reactants, and catalysts. A measure to determine quality.

When these factors are set to be less severe, the catalytic properties of the zeolite change from aromatic-producing properties to olefin-producing properties. According to a preferred embodiment of the invention, the severity of the contact can be reduced by contacting the feedstock with the catalyst at a partial pressure of the reactants below atmospheric pressure, this condition being partially under reduced pressure. This can be achieved by operating as a reactant or by diluting the reactant with a non-reactant.

The partial pressure of the reactant was set to 0.84 kg/Cd (12 p.s.i.
a) When carried out at pressures below, more than 85% of the raw reactants are converted to a hydrocarbon mixture containing steam and olefins. Non-reactive diluents used include water vapor, nitrogen, hydrogen, carbon dioxide, and paraffins having 5 or less carbon atoms.

A particularly preferable partial pressure value of the reactant is 0.06 to 0.53k.
9/Cr! i (0.8-7.5 p.s.i.a), but the total pressure during contact may be as high as 100 atmospheres. The temperature is typically 316-482°C (below 600-900°C) and the liquid hourly space velocity (LHSV) is preferably 0.5-482°C (below 600-900°C).
It is 200. In an extension of this embodiment, the conversion product is separated into olefin and gasoline, and the olefin is then separated (optionally after steam separation) into ZSM-5.
to produce a gasoline boiling range material characterized by a very low durene content (less than 2% by weight). In another embodiment of the invention,
The factor controlling the reaction is the catalyst, and the severity of the contact can be reduced by mixing the zeolite with at least the same weight of an inert solid diluent such as silica or alumina. The contact conditions in this embodiment are pressures of 0.2 to 30 atm and temperatures of 260 to 45
4°C (500-850'F), preferably 316-37
At 1°C (600-700'F), the weight hourly space velocity (W
IISV) is 1-100, preferably 2-40.
In these embodiments, it is preferred to convert at least a portion of the alcohol in the feed to ether prior to contacting.

In all embodiments of the invention, it is essential to use some kind of crystalline zeolite as active catalyst.

The catalyst used in this invention is a special type of zeolite that exhibits unique properties. These zeolites convert aliphatic hydrocarbons to aromatic hydrocarbons in commercially desirable yields and are generally used in alkylation reactions, isomerization reactions,
It is very effective in disproportionation reactions and reactions involving other aromatic hydrocarbons. Although they have a very low alumina content, ie a high silica/alumina ratio, they are very active, even when the silica/alumina ratio is 30 or more. Considering that the catalytic activity of zeolites generally depends on the framework of aluminum atoms and the cations bonded to these ammonium atoms,
It is a surprising fact that a catalyst with such a low alumina content has high activity. These zeolites used in the present invention are compatible with other zeolites such as type X and type A.
Remains crystalline for long periods even in the presence of water vapor at such high temperatures that the crystalline framework of the mold irreversibly disintegrates. Furthermore, even if carbonaceous deposits are formed, they can be easily removed by burning at a temperature higher than the normal temperature, and the activity can be restored. In many cases, this type of zeolite produces very low coke and can be regenerated many times. An important feature of the crystal structure of this type of zeolite is that the movement of molecules into and out of the crystal is regulated, and the free space inside the crystal has a hole size larger than about 5 angstroms, and the hole entrance is It is to have a size defined by the member ring.

Naturally, these 10-membered rings are formed by the usual arrangement of tetrahedra that form the anion framework of crystalline aluminosilicate, and the oxygen atoms themselves are bonded to silicon or aluminum in the center of the tetrahedron. bonded to atoms. Briefly, zeolites useful in the present invention have a silica/alumina ratio of at least about 12;
It has a structure that suppresses the entry and exit of molecules into the free space of the crystal. The silica/alumina ratio referred to herein can be determined by conventional analytical means.

This ratio is as close as possible to the ratio in the hard anionic framework of the zeolite crystals, excluding aluminum in the binder or cationic or other forms of aluminum in the channels. Silica/alumina ratio of at least 12
Zeolites having a silica/alumina ratio of at least about 40 are useful, with zeolites having higher silica/alumina ratios of at least about 40 being preferred. Particular preference is given to using zeolites with a silica/alumina ratio of at least 70. After activation, such zeolite has an internal crystalline adsorption ability that adsorbs n-hexane more strongly than water, and exhibits "hydrophobicity." This [hydrophobic] property is one of the advantages of the present invention. The zeolite catalyst used in the present invention freely adsorbs n-hexane and has a pore size of about 5 angstroms or greater.

Furthermore, the structure must inhibit the access of larger molecules. It is sometimes possible to determine whether a substance has such an inhibitory effect by knowing its crystal structure. For example, the entrance to the hole in the crystal is an oxygen atom.
Such zeolites are not a desirable type because molecules with cross-sectional areas larger than n-hexane are substantially excluded when formed by ring members. Zeolites in which the pore entrances are formed by 10-membered rings of oxygen atoms are desirable, but those in which the pores are too tight or clogged are ineffective. Zeolites whose pore entrances are formed by 12-membered rings of oxygen atoms generally do not provide sufficient inhibition to achieve the conversion reaction desired in the present invention; You can use fresh ones.
As an alternative to determining whether a zeolite has the desired inhibitory effect from its crystal structure, one can apply n-hexane and
- The "control index" can be easily determined by continuously passing a mixture of equal weight with methylpentane.

Samples of zeolite in the form of pellets or extrudates were first ground to coarse sand particle size and filled into glass tubes. Before testing the zeolite
Treat for at least 15 minutes with a stream of air at 1000[gamma]C. Helium was then passed through the zeolite and the temperature was raised to 288-55% so that the overall conversion was 10-60%.
Adjust to 10°C (550'F-950'F'). Hydrocarbons diluted with helium (helium/total hydrocarbon molar ratio 4/1) are deposited on zeolite at a liquid hourly space velocity of 1.
(i.e. at a volume of liquid hydrocarbon per unit volume of catalyst per unit time). After 20 minutes of flow, a sample of the effluent is taken and analyzed (conveniently by gas chromatography) to determine the fraction remaining unchanged of each of the two hydrocarbons.

The "control index" is calculated as follows.

The control index is approximately comparable to the ratio of the cracking rate constants of the two hydrocarbons.

Catalysts suitable for the present invention are those using zeolites having a control index of 1.0 to 12.0. The control indices of some representative zeolites (some of which are not within the scope of the present invention) are listed below. The aforementioned control index is very important and critical in defining a zeolite that represents an effective catalyst in the process of the present invention.

The nature of this factor and the technology cited allows a given zeolite to be tested under different conditions and may have different control indices. The control index varies slightly depending on the severity of the operation (conversion). It is therefore possible to select test conditions such that a plurality of control indices within or outside the range of 1 to 12 as defined above are obtained for a given zeolite. Therefore, the value ``control index'' used here includes the limit value without excluding it.

In other words, a zeolite that has been tested under the above test conditions and has a control index of 1 to 12 can be used in the present invention even if the control index is outside the range of 1 to 12 when tested under other conditions. Included in catalysts that can be used in Examples of these zeolites include ZSM-5, ZSM-11, Z
SM-12, ZSM-21, ZSM-35, ZSM-3
There is an 8th grade.

US Pat. No. 3,702,886 describes and claims ZSM-5 and is incorporated herein by reference.
ZSM-11 is described in detail in US Pat. No. 3,709,979, which is also incorporated herein.

ZSM-12 is described in detail in US Pat. No. 3,832,449, which is also incorporated herein.

French Patent No. 74-12078 is effective in the present invention.
The SM-21 zeolite composition and its manufacturing method are described in detail.

U.S. Patent Application No. 5280, filed November 29, 1974
No. 61 describes in detail the ZSM-35 zeolite composition useful in the present invention and its method of preparation, the contents of which are also introduced here.

U.S. Patent Application No. 5280, filed November 29, 1974
No. 60 describes in detail the ZSM-38 zeolite composition useful in the present invention and its method of preparation, the contents of which are also introduced here.

The X-ray diffraction pattern of ZSM-21 is similar to that of ZSM-35 and Z
It contains the X-ray diffraction pattern of SM-38.
Zeolites produced in the presence of organic cations are catalytically inactive since the free space of the internal crystals is occupied by the organic cations.

However, this is for example 538°C in an inert atmosphere.
(10001:') for 1 hour, then base exchanged with an ammonium salt, then 538°C (10
It can be activated by firing at 00T).

Although the presence of organic cations in the production raw material solution is not necessarily an essential condition for the production of this type of zeolite, the presence of these cations is advantageous for the production of this type of zeolite. Typically, this type of zeolite is base-exchanged using ammonium salts and then heated to about 1000'F in air for about 1
Those activated by firing for 5 minutes to about 24 hours are preferred. Sometimes natural zeolites are also subjected to various activation treatments,
This type of zeolite can be converted, for example, by means such as base exchange, steam treatment, alumina extraction and calcination, and these treatments can be carried out alone or in combination with the aforementioned treatment means.

Examples of natural zeolites that can be treated in this way are ferrielite, brilleusta monolith, and stilbite.
, datyaldite, epistilbite, hollandite, and clinoptilolite. Preferred crystalline aluminosilicate is ZSM-5,
ZSM-11, ZSM-12, ZSM-21, ZSM-
35 and ZSM-38, among which ZSM-5 is particularly preferred. The zeolite used as the catalyst of the present invention may be of hydrogen type or may be base-exchanged or impregnated to contain ammonium or metal cations.

After base exchange, it is desirable to calcine the zeolite. The metal cation to be present may be any metal cation from Group 1 to Group 1 of the periodic table. However, the first
In the case of Group A metals, the cation content should not be so great as to substantially interfere with the catalytic activity of the zeolites used in the present invention. For example, H-ZSM-5 with complete sodium exchange becomes significantly inert to the shape-selective conversion required by the present invention. In a preferred embodiment of the invention, the catalytically effective zeolites of the invention have a crystalline framework density (in dry hydrogen form) of substantially about 1.
．． 67/CC or higher.

It has been found that a zeolite that satisfies all of these three conditions is the most desirable. Accordingly, preferred catalysts of the invention have an inhibition index of about 1 to 12, a silica/alumina ratio of at least about 12, and a dry crystal density of substantially about 1.67/1.
It is made of zeolite that is CC or higher. The dry density of a material whose structure is known can be calculated from the number of silicon and aluminum atoms per 1000 cubic angstroms (1Ze01iteStrL by W. M. Meier).
(See page 19 of the article about zeolite structure). All the contents introduced here are 19
The SOcietyOfChemi in London in 1968
5ゞPrO published by callndustry
ceedingsOftheConferenceOn
It is described in Molecular Sieves.
If the crystal structure is not known, the density of the crystal framework can be determined by conventional pycnometer methods. For example, it can be measured by immersing a dried hydrogen-type zeolite in an organic solvent that is not adsorbed by zeolite crystals. It is possible to provide zeolites of this type with extremely high activity and stability with high crystalline anionic framework densities of about 1.6y/CC or higher. This high density must also have a relatively small amount of free space inside the crystal, which results in a more stable structure. This free space is important as a site of catalytic activity. The crystalline framework densities of several representative zeolites (some of which are not within the scope of the present invention) are shown below.

Mordenite 0.281.7 For the purposes of the present invention, the catalyst may be in any form such as pellets, beads or extrudates.

Binders such as clay, alumina and silica-alumina may also be present. In the process of the present invention, contact between the raw material and the solid catalyst is carried out by passing the raw material through a catalyst bed.

The catalyst bed may be of any fixed bed, fixed fluidized bed or moving bed type. In fixed bed or moving bed operation, the average particle size of the catalyst is 1.27 cTn (1/2 cm) in diameter.
2 inches) or more is acceptable, but generally the diameter is about 0.16~
It ranges from 0.64C7rL (0/16 to 1/4 inch). If a fluidized bed is employed, the catalyst must be so finely ground that it can be fluidized by the rising action of the vapors of the feedstock and diluent. Transport type catalyst beds, such as those used in fluidized catalytic cracking, may also be used. The effluent from the catalytic conversion step is treated by conventional means to separate the mixture of olefins into one or more olefin products depending on the intended use.

The alcohol used in the present invention may be produced from synthesis gas (i.e. a mixture of CO and H2 prepared from coal or natural gas), or by fermentation, or from petroleum distillates supplied in excess. Manufactured from minutes.

The resulting olefin products are converted to alkylates or aromatics and mixed with gasoline or separated for use as petroleum pharmaceuticals. That is, the present invention provides a new method for producing hydrocarbon petroleum drugs and fuels from raw materials other than petroleum. Additionally, the process of the present invention can be used to produce olefin feedstocks for converting methanol or dimethyl ether or both to low durene gasoline or gasoline blending feedstocks. As previously mentioned, the mixture of olefins produced by the present invention is predominantly ethylene, propylene, and butylene containing a small amount of benzene.

It may contain components other than those mentioned above, such as methanol, dimethyl ether, ethanol, and other substances. That is, it is a feature of the present invention that a mixture related to olefins is produced, and the product of the present invention is unrelated to the nature of the raw material, and the raw material cannot be recognized from the product. That is, the conversion reaction of the present invention is different from conventional dehydration reactions in which the olefin produced has a simple relationship with the raw material alcohol. An important feature of the present invention is that along with the olefins, highly useful hydrocarbons are produced as by-products.

Depending on the particular reaction conditions selected, components in the gasoline boiling range consisting of C5+ paraffins, olefins, naphthenes and aromatics are produced in varying amounts, including pentane, benzene and higher boiling substances. Substantially all of these products have boiling points below about 213°C (415'F), and therefore by-products in the gasoline boiling range will be recovered in producing olefins by the process of the present invention. Become. This gasoline byproduct tends to be rich in aromatic hydrocarbons and isoparaffins, thus resulting in a high octane number. When recovered, C5+~213℃ (4
The 15'F) fraction is used directly as gasoline or as a raw material for blending high octane gasoline. Although it is known to convert methanol or dimethyl ether or both into gasoline as described in DE 24 38 252, the gasoline obtained by this known process has a very high durene content, which is undesirable. .

Dulen is undesirable in high concentrations in gasoline because it can crystallize and cause problems in the engine or reservoir fuel supply system. The by-product gasoline obtained in the present invention has a low durene content, containing less than about 2% by weight durene. One of the characteristics of the present invention is that it is possible to obtain a gasoline produced in X, China with a low durene content.
It is one. In fact, in most cases the durene content is substantially less than 2% by weight, ie less than about 1% by weight, and such amounts do not cause any problems. Durene is formed when unconverted methanol and/or dimethyl ether interacts with aromatic hydrocarbons, so this problem is only a problem with feedstocks consisting of methanol and/or dimethyl ether. In another embodiment of the invention, the olefins obtained by converting feedstocks consisting of methanol or dimethyl ether or both are subsequently converted in an aromatization step to produce additional gasoline boiling range compounds. , the overall production of gasoline can be increased, and the durene content of the gasoline thus obtained is substantially less than about 2%.

This method of obtaining low durene gasoline from methanol and/or dimethyl ether by a two-step process operates to substantially complete conversion of methanol and/or dimethyl ether in the first step. It is most effective when methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol and tertiary-butanol, etc. alone or in mixtures with each other or with simple ethers of said alcohols such as dimethyl ether; Can be used as Preferred reactants are methanol, dimethyl ether and mixtures thereof and such reactant compositions containing at least 10% by weight of methanol or dimethyl ether. For purposes of use in the present invention, the purity of the reactants need not be higher than normal technical purity. It is also a feature of the invention that other oxygen compounds such as esters that may be present in the feedstock are often converted to hydrocarbons along with the alcohol. According to embodiments characterized in that the conversion is carried out at subatmospheric partial pressures (for alcohols), substantially complete conversion of alcohols or ethers or both to hydrocarbons is carried out without recirculation.

It will be understood that subatmospheric partial pressure as used herein refers to the partial pressure of the feedstock measured and calculated at the maximum temperature obtainable in the reactor while the conversion reaction is taking place. Therefore, alternating between a specific partial pressure at the inlet of the reaction zone (where the inlet of the reaction zone is the place where the feedstock first meets the catalyst), i.e. the inlet partial pressure of the feedstock or the maximum partial pressure of the feedstock in the reaction zone. Measure and fix the amount.
It should also be understood that the partial pressures described herein are "partial pressures for alcohol." That is, even if pure ether were charged alone, the partial pressure with respect to alcohol would correspond to twice its actual partial pressure.
Therefore, it is the same whether the alcohol is charged under the same specific partial pressure or the ether is charged alone, and the olefin obtained in both cases will be under the same partial pressure. If the inlet partial pressure of the raw material is below atmospheric pressure, that is, if the inlet partial pressure of the raw material is lower than 1.1 kg/Cd (15 psia), then the inlet partial pressure of the raw material is 1.1 kg/Cd (15 psia).
An improvement is made in the selectivity of olefin production compared to the procedure described above. Improvements in selectivity are generally made at the expense of lower yields of aromatic and/or paraffinic hydrocarbons. However, selectivity improvement increases as the inlet partial pressure is reduced, and the greatest benefits of the present invention are achieved when operating at inlet partial pressures below about 12 psia. The preferred range of the inlet partial pressure of the raw material is about 0.007 kg/Cd to about 0.84
k9/Cd (about 0.1 psia to about 12 psia), with a particularly preferred range of about 0.06 k9/Cd to about 0.5
3kg/Cd (approximately 0.8 psia to approximately 7.5 psia)
It is. The inlet partial pressure of the feedstock for alcohol is approximately 0.84 kg by applying a partial vacuum to the reactor or by adding an appropriate amount of diluent to the feedstock.
/Cd (12 psia) or less. The diluent used herein may be any substantially inert substance that is a gas or vapor at the reaction temperature. Examples of such inert substances include gaseous nitrogen, carbon dioxide, carbon monoxide, hydrogen and water vapor. Steam has the advantage of being easily separated from the olefin product, but under certain conditions it reduces the activity of the catalyst somewhat. Hydrogen should not be used under conditions that promote hydrogenation of the olefin product. Paraffinic hydrocarbons having 1 to 8, preferably 1 to 5 carbon atoms may also be used.

Methane and ethane are substantially inert under the reaction conditions of this process, especially at higher space velocities. The propane to pentane hydrocarbons are resistant to conversion under most of the reaction conditions described below. These hydrocarbon diluents may be supplied from by-products of conversion reactions of alcohols and/or ethers, but it is important that the diluents are substantially olefin-free. If a diluent is used, the overall pressure in the reaction zone can range from below atmospheric pressure to about 1
It can be varied up to 0.05 kg/y (150 psia).

It is a feature of the present invention that the diluent serves to remove the heat of reaction generated in the more exothermic alcohol or ether conversion reactions, ie, the conversion reactions for the preferred methanol and dimethyl ether feeds. Preferred overall pressure in the reaction zone when using diluent 1.1k
9/Cri~35.2k9/Cd (15psia~50
0 psia). In the method of the invention, the temperature in the reaction zone is between about 260°C (5001?) and about 538°C.
(1000'F), preferably about 316°C (60
0'F) to about 482C (900'F).

A particularly preferred temperature range is from about 343°C (650'F) to about 45'C (850'F). The raw material is 0.0 on the catalyst
It is flowed at a rate of 5 to 200 LHSV (volume of liquid feedstock per unit volume of catalyst per unit time) J.

However, it is preferred to operate in the range of about 1 to about 50 LHSV. The advantages of the present invention in producing olefins with improved selectivity even when operating under conditions where not all of the feedstock is converted are undeniable, and at least 85% by weight of the alcohol or ether or both are converted into hydrocarbons. It is desirable to select the temperature, feed rate and inlet partial pressure such that the alcohol and/or ether is converted, in particular at least 95% by weight, i.e. substantially completely, of the alcohol and/or ether. It is preferable. Furthermore, it is desirable to set conditions such that the raw material is converted into a hydrocarbon whose main fraction is olefin within the above-mentioned specific range. Since the reactivity varies depending on the type of raw material, it is difficult to select the desired conditions accurately, but generally the inlet partial pressure of the raw material is set to about 0.53 k9/Cd (7.5 ps
ig) or less, and the feed rate of raw materials is about 1.0 to about 20L.
Highly desirable results can be obtained by using HSV. Example 1 50 m' of hydrogen-type zeolite ZSM-5 finely ground to pass through a 325 mesh (US standard sieve)
was intimately mixed with 2.5y of Vycor (silica) of 50-80 mesh (US standard sieve).

Methanol was passed through the octopus catalyst bed maintained at a temperature of 343° C. (650 T) at a weight hourly space velocity of 30.

The conversion rate of methanol to hydrocarbons was 54%. The resulting hydrocarbon conversion product was analyzed as follows. Example 2 Hydrogen-type zeolite ZSM-5, which has been crushed so finely that it can pass through 100 mesh (US standards), was pulverized at 538°C (10
100 mesh pre-fired at 00'F (US standards)
was intimately mixed with alumina to obtain a mixture containing 10% by weight of SM-5 and 90% by weight of alumina.

The resulting mixture was pelletized into 14-30 meshes (US standards). methanol at 343℃ (650℃)
'F) at a weight-hourly space velocity of 10~
I made it 50 and passed.

The conversion rate of methanol to hydrocarbons was 60%. The resulting hydrocarbon conversion product was analyzed as follows. Example 3 Hydrogen-type zeolite ZSM-5, which has been ground so finely that it can pass through a 325 mesh (US standard) sieve, is heated to 538°C.
(1000'1:') 100 meshes (
Thoroughly mix 1ηSM-5 with alumina (US standard).
A mixture containing 0% by weight and 90% by weight alumina was obtained.

The resulting mixture was pelletized into 14-100 meshes (US standards). methanol at 343℃ (6
A weight hourly space velocity of 40
I set it to ~100 and passed.

The conversion rate of methanol to hydrocarbons was 60%. The resulting hydrocarbon conversion product was analyzed as follows. Examples 4 to 14 (Example 5 is a comparative example) A part SM-5 extruded catalyst containing 35% alumina binder was charged into a stainless steel reactor with the addition of an electric resistance heater, and the reaction temperature was raised to about 42°C. The temperature was adjusted to 800'F.

The HZSM-5 used had a silica/alumina ratio of 70. Methanol was flowed over the catalyst by a pump at the following LHSV. A mass flow meter was used to supply the gas. Liquid or gaseous products or both were collected in a wet ice trap and a dry ice trap. Gaseous products were collected directly into empty graduated containers if the total volume was less than 5 liters. For high gas dilution operations, the reactor effluent was scraped through a liquid nitrogen trap and measured with a wet test meter. At the end of the run, the condensed gas in the nitrogen trap as well as the gas from other traps was measured in a graduated vessel. Analysis of all products was performed by gas chromatography.

The results obtained in these examples demonstrate the effect of subatmospheric partial pressures and the use of diluents and are reported in Table A below. In this table, the partial pressure of methanol indicates the inlet partial pressure (absolute pressure). Examples 15 to 17 (Example 16 is a comparative example) In these examples, HZs similar to those used in Examples 4 to 14 were used.
Using SM-5 catalyst, the conversion temperature was approximately 427°C (800°C).
The reaction was carried out under the same conversion conditions as Examples 4-14, except that the reaction temperature was maintained at about 37'C* (700'F) instead of 'F).

The results obtained are shown in Table B below. 40-140 HZSM-5 catalyst was used.

All conversion temperatures were about 427°C (below 800°C) and other operating conditions were the same as Examples 4-14. The results obtained are shown in Table C below. Example 23 Ethanol is heated at approximately 427°C (800'F') at an inlet partial pressure of 0.5 atm (absolute) and at a feed rate of 12 LHSV.
Contacted with ZSM-5 catalyst.

Using nitrogen diluent to bring the total pressure to about 1 atm (absolute)
And so. Substantially complete conversion of the ethanol resulted in a hydrocarbon mixture having the following composition. Example 25 (Reference Example) The product of Example 6 (Table A) is partially condensed to recover water and 47.9% by weight of hydrocarbons as C5 gasoline.

The remaining C4-hydrocarbons were heated to 371°C (700°C) without fractional distillation.
(lower), converted on a model M-5 at 1 atm and 1 LHS. The product obtained had the following composition. Example 24 11ZSM-11 was used as catalyst.

Methanol was fed at an inlet partial pressure of 0.5 atm (absolute) and nitrogen diluent at 0.5 atm. Reaction temperature is 427℃
The conversion reaction was carried out at (800'F) with an LHS of 12 and substantially all (99%) of the methanol was converted to hydrocarbons. The total effluent obtained by the procedure of Examples 4-14 was analyzed and had the following composition. This second
By separating the C5+ Ganlin obtained from the step conversion and combining it with the initially prepared gasoline, its yield increases by about 45%, and the durene content goes from about 0.62% by weight to about 0. It decreased to .47% by weight.

Example 26 (Reference Example) The reactor effluent in Example 9 (Table A) was compressed to 12 atmospheres and 1I2 at a rate of 1LHSV based on hydrocarbons.
A second reactor containing SSM-5 was fed and the total pressure was brought to 12
The reaction was carried out at a temperature of 37 FC (700'F) at atmospheric pressure.

Claims (1)

[Scope of Claims] 1 Alcohol or ether having 4 or less carbon atoms per alkyl group, or both, with a control index of 1.0 to 12.0 and a silica/alumina ratio of 12 to 30
00, the crystal density in the dry hydrogen form is essentially 1
．． A process for converting to olefins by contacting with a catalyst containing a crystalline aluminosilicate zeolite of 6 g/cc or more, comprising: (a) reducing the partial pressure of the alcohol or ether, or both, to less than atmospheric pressure during said contact; or (b) using as a catalyst a zeolite mixed with at least an equal weight of zeolite and an inert solid diluent; thereby at a sufficiently low severity to reduce the aromatization activity of the catalyst. A process for converting alcohols or ethers or both into olefins, characterized in that contact is carried out. 2. The method according to claim 1, wherein the contact is carried out while maintaining the partial pressure of alcohol or ether or both at a level lower than 0.84 kg/cm^2. 3. The method according to claim 1 or 2, wherein the partial pressure of the reactant is made lower than atmospheric pressure by diluting the raw materials. 4. The method according to claim 3, wherein the raw material is diluted with steam, nitrogen, hydrogen, carbon dioxide, or paraffin having 5 or less carbon atoms. 5 The partial pressure of the reactant is 0.06 to 0.53 kg/cm^2
The method according to any one of claims 1 to 4. 6 Total pressure below 100 atm, liquid hourly space velocity 0.0
The method according to any one of claims 1 to 4, wherein the contacting is carried out at a temperature of 316 to 482°C. 7. A process according to any one of claims 1 to 6, in which the olefin product is separated from the gasoline product after contacting. 8. The method of claim 1, wherein the alcohol is at least partially converted to an ether before contacting. 9 Claim 1 in which the solid diluent contains silica
The method described in section. 10. The method of claim 1, wherein the solid diluent contains alumina. 11. The method according to claim 9 or 10, wherein the contact is carried out at a pressure of 0.2 to 30 atmospheres. 12. Claim 9 or 10 in which the contact is carried out at a temperature of 260 to 454°C and a space velocity of 1 to 100 weight hours.
The method described in section. 13. A method according to claim 9 or claim 10, wherein the contacting is carried out at a temperature of 316-371°C and a space velocity of 2-40 weight hours. 14 Zeolite is zeolite ZSM-5, ZSM-1
1, ZSM-12, ZSM-35 or ZSM-38. 15. The method according to any one of claims 1 to 14, wherein the zeolite is a hydrogen type. 16. A method according to any of claims 1 to 15, wherein each alkyl group contains one carbon atom.